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万伯 顺 bswan@dicp.ac.cn

杂环合成中的 环加成与环化反应. 万伯 顺 bswan@dicp.ac.cn. Why Cycloadditon ?. Advantages :  Two C-C bonds & One C-N bond simultaneously  High atom efficiency Problems :  Regioselectivity  Chemoselectivity.

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万伯 顺 bswan@dicp.ac.cn

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  1. 杂环合成中的 环加成与环化反应 万伯顺 bswan@dicp.ac.cn

  2. Why Cycloadditon? Advantages:  Two C-C bonds & One C-N bond simultaneously  High atom efficiency Problems: Regioselectivity  Chemoselectivity D. Siegel et al, J. Am. Chem. Soc. 2010, 132, 5924.

  3. Why Iron? US$ per mol Organometallics, 2002, 21, 2578 Iron(I) complex 2011 Wan Iron(0) complex Organometallics, 1996, 15, 2713 Iron (0.02 US$/mol)

  4. Iron Catalytic System

  5. Problems and Solutions Holland’s investigation: The binding affinity toward the low-valentiron: Holland, P. L. et al. Inorg. Chem. 2006, 45, 5742.

  6. Problems and Solutions

  7. Cycloaddition of Diynes and UnactivatedNitriles

  8. Cycloaddition of Diynes and Unactivated Nitriles (Continued) Cycloaddition of Tetrayne

  9. All-intramolecularCycloaddition Cycloaddition of Alkynenitrile and Alkyne

  10. Control Experiments

  11. Possible Pathways to Form Pyridines WithWang, C. X.Angew. Chem. Int. Ed. 2011, 50, 7162

  12. a 5 mol% catalyst, 5 equiv nitrile b 10 mol% catalyst, 2 equiv nitrile WithWang, C. X.J. Org. Chem. 2013, 78, 3065

  13. [2+2+2] Cycloaddition in Pure Water

  14. [2+2+2] Cycloaddition in Pure Water With Xu, F. ChemSusChem. 2012, 5, 854

  15. New Cycloaddition of Oximes and Diynes [2+2+2] Cycloaddition [Ru] Catalyst H2O Aldehyde Oxime

  16. New Cycloaddition of Oximes and Diynes Rearrangement of oximes into amides Reactivity of the C=N double bond Water generated from cycloadducts

  17. New Cycloaddition of Oximes and Diynes

  18. New Cycloaddition of Oximes and Diynes Key Point With Xu, F.Chem Eur J 2013, 19, 2252.

  19. Nickel-catalyzed [3 + 2] cycloaddition of diynes with MAs Chem. Commun. 2013, ASAP C3CC41061G C-C bond cleavage N-C bond cleavage

  20. Proposed mechanism

  21. Synthesis of Pyrroles via Cyclization Building blocks 双键 叁键 What ? 电子/空间调控基团 杂原子

  22. Synthesis of Pyrroles via Cyclization × DMF, Ar 140 oC × Ts = p-CH3PhSO2-

  23. Synthesis of Pyrroles via Cyclization WithXin, X. Y. Angew. Chem. Int. Ed. 2012, 51, 1693.

  24. Mechanism Study "α" Migration

  25. Mechanism Study "β" Migration

  26. Mechanism Study Crossover Experiment

  27. Crossover Experiment Competition Experiment

  28. Cyclizationof Aza-enynes Catalyst + 2a(%) J. Org. Chem. 2013 ASAP jo400387b

  29. Cyclizationof Aza-enynes J. Org. Chem. 2013 ASAP jo400387b

  30. Mechanism Study

  31. Proposed Mechanism J. Org. Chem. 2013 ASAP jo400387b

  32. Another example of cyclization with Ts migration With Yu, X. Z. J. Org. Chem. 2013, jo4004635

  33. Other important finding Xingwei Li,* Boshun Wan*, Angew. Chem. Int. Ed.2013, 52, 2577

  34. 环加成与环化反应小结 六元环: (1) JOCjo400387b (2)Unpublished results 五元环:ACIE, 2012, 51, 1693 四元环: Unpublished results 三元环:Unpublished results

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